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EP2219843B1 - Method for producing molded parts having reduced deposit formation - Google Patents

Method for producing molded parts having reduced deposit formation Download PDF

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Publication number
EP2219843B1
EP2219843B1 EP08855931A EP08855931A EP2219843B1 EP 2219843 B1 EP2219843 B1 EP 2219843B1 EP 08855931 A EP08855931 A EP 08855931A EP 08855931 A EP08855931 A EP 08855931A EP 2219843 B1 EP2219843 B1 EP 2219843B1
Authority
EP
European Patent Office
Prior art keywords
weight
thermoplastic molding
parts
moldings
acrylonitrile
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP08855931A
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German (de)
French (fr)
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EP2219843A2 (en
Inventor
Wolfgang Fischer
Moritz Ehrenstein
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Ineos Styrolution Ludwigshafen GmbH
Original Assignee
Styrolution GmbH
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Priority to EP08855931A priority Critical patent/EP2219843B1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59

Definitions

  • the invention relates to processes for the production of molded parts by molding thermoplastic molding compositions F with reduced deposit formation on the forming tool.
  • the present invention relates to the use of molding compositions F in the process of the invention and moldings which can be produced by the process according to the invention.
  • thermoplastic molding compositions In the prior art, the most diverse thermoplastic molding compositions and methods for the production of moldings by shaping these thermoplastic molding compositions are described.
  • plastics In these molding processes plastics are melted and pressed through nozzles, for example, in molds or on conveyor belts.
  • An often occurring problem in these molding processes is the formation of moldings on the forming tools, preferably in the sprue and vent areas, and / or on the mold surfaces.
  • the pads are made of plastic waste. You can e.g. from impurities or auxiliaries from the production process or from plastics-compatible additives such as flame retardants, lubricants or pigments.
  • These moldings can lead to a deterioration in the surface quality of the molded parts, problems in printing or bonding and poor impression of cavities.
  • thermoplastic molding compositions in which graft rubber dispersions are not coagulated by the addition of acids or salts as coagulants but by a special mechanical shear precipitation.
  • impurities in the thermoplastic molding compositions which can lead to an impairment of the product properties, largely avoided.
  • the contents of any salts, acids or impurities are not disclosed. Information on the production of molded parts from these thermoplastic molding compounds is just as little made.
  • ABS molding compositions containing 0.001 to 0.3 wt .-% of special salts, including certain magnesium and calcium compounds.
  • special salts including certain magnesium and calcium compounds.
  • the processing of these ABS molding compositions at a higher temperature to form a molded article should be possible with reduced discoloration and thus an improved inherent color of the polymers. Further possible difficulties in the production of moldings, in particular a reduction in the formation of moldings, are not discussed.
  • the in WO 02/42347 disclosed invention is the object of preventing moldings in the production of molded parts.
  • the solution to this problem is according to this document in the addition of a pH buffer system after completion of the polymerization of the elastomeric polymer.
  • the proportions of any magnesium or calcium compounds in the thus prepared thermoplastic molding compositions are not disclosed.
  • thermoplastic molding compositions in injection molding to moldings a uniform surface without discoloration, efflorescence and outgassing, if the flame retardant used has a magnesium content of 50 mg / kg or less. That the magnesium content of the entire thermoplastic molding composition with regard to the solution of the underlying task could have a meaning, the Scripture is nowhere to be found.
  • the object of the present invention was to provide processes for the production of molded parts by shaping thermoplastic molding compositions which, compared to the known processes, have a reduced formation of deposits on the shaping tool and / or the molding surface.
  • thermoplastic molding compositions F magnesium and / or calcium compounds in an amount of 0 mg / kg to 100 mg / kg (calculated as the sum of mg mg and mg Ca per kg of thermoplastic Molding composition F and determined by means of inductively coupled plasma atomic emission spectrometry (ICP-AES)).
  • the processes according to the invention for producing molded parts by molding thermoplastic molding compositions F have a reduced deposit formation on the forming tool and / or the molding surface compared to the known processes.
  • thermoplastic molding compositions F are used as the starting material, the up to 75 mg / kg, in particular from 5 mg / kg to 50 mg / kg (in each case calculated as the sum of mg mg and mg Ca per kg of thermoplastic molding material F)
  • the magnesium and calcium contents of the thermoplastic molding compositions are inductive with atomic emission spectrometry coupled plasma (ICP-AES); this method is known to the person skilled in the art and described in the literature.
  • Preferred magnesium and / or calcium compounds are magnesium oxide, magnesium hydroxide, magnesium sulfate, magnesium carbonate, magnesium stearate, calcium hydroxide, calcium carbonate, calcium sulfate, calcium stearate or mixtures of two or more of the compounds mentioned. Particularly preferred are magnesium sulfate and magnesium stearate.
  • thermoplastic molding compositions F can in principle contain all thermoplastic polymers known to the person skilled in the art and described in the literature; also mixtures of several of these thermoplastic polymers are suitable.
  • thermoplastic molding compositions F preferably usable thermoplastic polymers are one or more polymers selected from the group ASA, ABS, polyamides and polyesters.
  • Preferred impact-modified vinylaromatic copolymers are impact-modified copolymers of vinylaromatic monomers and vinyl cyanides (SAN).
  • SAN vinylaromatic monomers and vinyl cyanides
  • ASA polymers and / or ABS polymers are preferably used as the impact-modified SAN, as well as (meth) acrylate-acrylonitrile-butadiene-styrene polymers ("MABS", transparent ABS), but also blends of SAN, ABS, ASA and MABS other thermoplastics such as polycarbonate, polyamide, polyethylene terephthalate, polybutylene terephthalate, PVC, polyolefins.
  • ASA polymers are generally understood to be impact-modified SAN polymers in which rubber-elastic graft copolymers of vinylaromatic compounds, in particular styrene, and vinyl cyanides, in particular acrylonitrile, are present on polyalkyl acrylate rubbers in a copolymer matrix of, in particular, styrene and / or .alpha.-methylstyrene and acrylonitrile.
  • ASA polymers are known to the person skilled in the art and described in the literature, for example in DIN EN ISO 6402-1 DE of February 2003.
  • ABS polymers are generally understood to be impact-modified SAN polymers in which diene polymers, in particular 1,3-polybutadiene, are present in a copolymer matrix of, in particular, styrene and / or ⁇ -methylstyrene and acrylonitrile. ABS polymers are known to the person skilled in the art and described in the literature, for example in DIN EN ISO 2580-1 DE of February 2003.
  • thermoplastic polymers are partially crystalline polyolefins such as homopolymers or copolymers of ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methyl-1-penten-1 and ethylene copolymers with vinyl acetate, vinyl alcohol , Ethyl acrylate, butyl acrylate or methacrylate.
  • HDPE high-density polyethylene
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • PP polypropylene
  • EVA ethylene-vinyl acetate copolymer
  • EVA ethylene-acrylic Copolymer used.
  • thermoplastic polymers are polycarbonates.
  • the polycarbonates preferably have a molecular weight (weight average M w , as determined by gel permeation chromatography in tetrahydrofuran against polystyrene standards) in the range of 10,000 to 60,000 g / mol. They are eg according to the procedures of DE-B-1 300 266 by interfacial polycondensation or according to the method of DE-A-1 495 730 by reaction of diphenyl carbonate with bisphenols available.
  • Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, generally referred to as bisphenol A, as hereinafter.
  • bisphenol A instead of bisphenol A, it is also possible to use other aromatic dihydroxy compounds, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxyniphenyl ether.
  • aromatic dihydroxy compounds in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxyniphenyl ether.
  • Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mol% of the abovementioned aromatic dihydroxy compounds.
  • Particularly suitable polycarbonates are those which contain units which are derived from resorcinol or Alkylresorcinolestern, as for example in WO 00/61664 . WO 00/15718 or WO 00/26274 to be discribed; These polycarbonates are marketed, for example, General Electric Company under the trademark SollX ®. Copolycarbonates according to the US-A 3,737,409 be used; Of particular interest are copolycarbonates based on bisphenol A and di- (3,5-dimethyl-dihydroxyphenyl) sulfone, which are characterized by a high heat resistance. It is also possible to use mixtures of different polycarbonates.
  • thermoplastic molding compositions F any aromatic or aliphatic thermoplastic polyurethane is preferably suitable as the thermoplastic polymer, preferably amorphous aliphatic thermoplastic polyurethanes which are transparent are suitable.
  • Aliphatic thermoplastic polyurethanes and their preparation are known in the art, for example from EP-B1 567 883 or DE-A 10321081 , And commercially available, for example under the brand names Texin ® and Desmopan ® Bayer Aktiengesellschaft.
  • thermoplastic molding compositions F may contain all known in the art and described in the literature buchstofpfblichen additives. These plastic-compatible additives preferably contain substantially no magnesium and / or calcium compounds. The term "essentially none" means that the content of magnesium and / or calcium compounds in the plastic-compatible additives is below the detection limit of the ICP-AES analysis method.
  • Plastic additives for the purposes of the present invention are, for example, stabilizers and antioxidants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, dyes and pigments and plasticizers and fibers, for example glass fibers or carbon fibers.
  • Oxidation retarders and heat stabilizers that can be added to the thermoplastic molding material F according to the invention are, for. B. halides of metals of Group I of the Periodic Table, z. For example, sodium, potassium, lithium halides. Furthermore, zinc fluoride and zinc chloride can be used. Further, sterically hindered phenols, hydroquinones, substituted members of this group, secondary aromatic amines, optionally in conjunction with phosphorus-containing acids or their salts, and mixtures of these compounds, preferably in concentrations up to 1 wt .-%, based on the weight of the thermoplastic Molding compounds F, can be used.
  • UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benzophenones, which are generally used in amounts of up to 2% by weight, based on the weight of the thermoplastic molding compositions F.
  • Lubricants and mold release agents which can generally be added in amounts of up to 1% by weight, based on the weight of the thermoplastic molding compositions F, of stearic acid, stearyl alcohol, stearic acid alkyl esters and amides and esters of pentaerythritol with long-chain fatty acids.
  • stearic acid stearyl alcohol
  • stearic acid alkyl esters stearic acid alkyl esters and amides and esters of pentaerythritol with long-chain fatty acids.
  • B. distearyl ketone used.
  • Particularly suitable according to the invention are stearates and also N, N'-ethylene-bisstearamide.
  • glass fibers it is possible in the molding compositions F according to the invention to use all glass fibers known to the person skilled in the art and described in the literature (see, for example, US Pat Milewski, JV, Katz, HS "Handbook of Reinforcements for Plastics", p. 233 et seq., Van Nostrand Reinholt Company Inc, 1987 ).
  • thermoplastic molding compositions F can be prepared by processes known to the person skilled in the art and described in the literature, in particular by melt-mixing of the thermoplastic polymers, the magnesium and / or calcium compound and optionally the plastic-compatible additives in a screw extruder.
  • twin-screw extruders which can be rotating and intermeshing in the same direction, as well as counter-intermeshing and non-combing, can be used. Preference is given to using twin-screw extruders. Particularly preferred are co-rotating, intermeshing twin-screw extruders. Suitable screw extruders are, for example, in Saechtling, Plastic Paperback, Hanser Verlag, Kunststoff, Vienna, Issue 26, 1995, pages 191-246 , described.
  • the molding is preferably carried out by extrusion, in particular extrusion into granules, films, sheets, strands or profiles, or by injection molding into moldings; Particularly preferred is the injection molding into moldings.
  • extrusion and injection molding mentioned and the devices used are known as such to the person skilled in the art and described in the literature.
  • thermoplastic molding compositions F containing magnesium and / or calcium compounds in the abovementioned amount in the processes according to the invention achieves a reduced formation of deposits on the shaping tool compared to the known methods of shaping.
  • Particularly preferred molded parts which can be produced by the process according to the invention are, for example, household articles, electronic components, medical devices, automotive components and building materials, in particular injection-molded chip cards and toy building blocks, housings for electrical and electronic parts, for example food processors, razors, telephones, vacuum cleaners Monitor enclosures, keyboards, electric lawn mowers, toy trains, washing machines, dishwashers, refrigerators, automotive interior parts, and automotive exterior applications such as hubcaps, exterior mirrors (colored, painted or galvanized), grills and spoilers.
  • housings for electrical and electronic parts for example food processors, razors, telephones, vacuum cleaners Monitor enclosures, keyboards, electric lawn mowers, toy trains, washing machines, dishwashers, refrigerators, automotive interior parts, and automotive exterior applications such as hubcaps, exterior mirrors (colored, painted or galvanized), grills and spoilers.
  • the moldings which can be produced by the process according to the invention have an improved surface quality as a result of the reduced deposit formation during shaping compared to moldings which can be produced by known processes.
  • Molding compounds preceded by "V-" are not inventive and are for comparison.
  • the preparation of the butadiene graft rubber B was carried out until completion of the graft copolymerization as described in the preparation of the butadiene graft rubber A.
  • the subsequent precipitation of the butadiene graft rubber B from the dispersion was not carried out by means of magnesium sulfate solution but by freeze precipitation on a flake ice machine, followed by sintering for 30 minutes 121 ° C and subsequent cooling to 60 ° C. Subsequently, water was spun on a sling.
  • the thus pre-dehydrated butadiene graft rubber (residual moisture content about 30 wt .-%) was finally dried in a stream of warm air.
  • the preparation of the acrylate graft rubber I was carried out until completion of the graft copolymerization as described in the preparation of the acrylate graft rubber H.
  • the subsequent precipitation of the acrylate graft rubber I from the dispersion was not carried out by means of magnesium sulfate solution but by freeze precipitation on a flake ice machine, followed by sintering at 121 ° C. for 30 minutes and subsequent cooling to 60 ° C. Subsequently, water was spun on a sling.
  • the pre-dehydrated acrylate graft rubber residual moisture content about 30% by weight was finally dried in a stream of warm air.
  • 48 parts by weight of the dried butadiene graft rubber A were mixed with 52 parts by weight of granules of a commercially available styrene-acrylonitrile copolymer having an acrylonitrile content of 24 wt .-% and a viscosity of 64 at 250 ° C on a ZSK 30 twin-screw extruder extruded and granulated.
  • the content of magnesium in the granules was 510 mg / kg, the content of calcium in the granules was ⁇ 3 mg / kg.
  • 48 parts by weight of the dried butadiene graft rubber B were mixed with 52 parts by weight of granules of a commercially available styrene-acrylonitrile copolymer having an acrylonitrile content of 24 wt .-% and a viscosity of 64 at 250 ° C on a ZSK 30 twin-screw extruder extruded and granulated.
  • the content of magnesium in the granules was ⁇ 3 mg / kg
  • the content of calcium in the granules was ⁇ 3 mg / kg.
  • 20 parts by weight of the dried butadiene graft rubber B were mixed with 20 parts by weight of a granule of a commercial styrene-acrylonitrile copolymer having an acrylonitrile content of 24 wt .-% and a viscosity number of 64 and 60 parts by weight of an ⁇ - Methyl styrene-acrylonitrile copolymer having an acrylonitrile content of 30 wt .-% and a viscosity number of 57 at 250 ° C on a twin-screw extruder ZSK 30 extruded and granulated.
  • the content of magnesium in the granules was ⁇ 3 mg / kg
  • the content of calcium in the granule was ⁇ 3 mg / kg.
  • the dried acrylate graft rubber H 45 parts by weight of the dried acrylate graft rubber H were mixed with 50 parts by weight of granules of a commercial styrene-acrylonitrile copolymer having an acrylonitrile content of 19 wt .-% and a viscosity number of 100 at 250 ° C on a ZSK 30 twin-screw extruder extruded and granulated.
  • the content of magnesium in the granules was 370 mg / kg
  • the content of calcium in the granules was ⁇ 3 mg / kg.
  • molding compound FK was like that of the comparative molding compound VFJ, but instead of the acrylate graft rubber H, the acrylate graft rubber I was used.
  • the content of magnesium in the granules was ⁇ 3 mg / kg, the content of calcium in the granules was ⁇ 3 mg / kg.
  • the dried acrylate graft rubber H 45 parts by weight of the dried acrylate graft rubber H were mixed with 55 parts by weight of granules of a commercially available styrene-acrylonitrile copolymer having an acrylonitrile content of 35 wt .-% and a viscosity number of 80 at 250 ° C on a ZSK 30 twin-screw extruder extruded and granulated.
  • the content of magnesium in the granules was 360 mg / kg
  • the content of calcium in the granules was ⁇ 3 mg / kg.
  • molding compound F-M was carried out as that of the comparative molding compound V-F-L, but instead of the acrylate graft rubber H, the acrylate graft rubber I was used.
  • the content of magnesium in the granules was ⁇ 3 mg / kg, the content of calcium in the granules was ⁇ 3 mg / kg.
  • 20 parts by weight of the dried acrylate graft rubber H were mixed with 20 parts by weight of a granules of a commercially available styrene-acrylonitrile copolymer having an acrylonitrile content of 35 wt .-% and a viscosity number of 80 and 60 parts by weight of granules commercially available polycarbonate, Makrolon ® 2800 from Bayer MaterialScience AG, extruded 30 at 250 ° C on a twin-screw extruder ZSK and granulated.
  • the content of magnesium in the granules was 135 mg / kg
  • the content of calcium in the granules was ⁇ 3 mg / kg.
  • 8.5 parts by weight of the dried acrylate graft rubber H were mixed with 8.5 parts by weight of the dried acrylate graft rubber I, 13 parts by weight of a granule of a commercially available styrene-acrylonitrile copolymer having an acrylonitrile content of 19 wt. % and a viscosity number of 70 and 60 parts by weight of granules of a commercial polycarbonate, Makrolon ® 2800 of Bayer Material Science AG, extruded at 250 ° C on a twin-screw extruder ZSK 30 and granulated.
  • the content of magnesium in the granules was 36 mg / kg
  • the content of calcium in the granules was ⁇ 3 mg / kg.
  • 30 parts by weight of the dried acrylate graft rubber I were with 10 parts by weight of a granulate of a commercially available styrene-acrylonitrile copolymer having an acrylonitrile content of 19 wt .-% and a viscosity number of 70 and 60 parts by weight of a Granules of a commercial polycarbonate, Makrolon ® 2800 from Bayer Material Science AG, extruded at 250 ° C on a twin-screw extruder ZSK 30 and granulated.
  • the content of magnesium in the granules was ⁇ 3 mg / kg
  • the content of calcium in the granules was ⁇ 3 mg / kg.
  • the magnesium and calcium contents of the abovementioned molding compositions F and of the comparative molding compounds VF were determined by burning a respective balanced amount of the relevant plastic granulate, subjecting the combustion residue to soda-borax digestion, then dissolving the digestion residue in hydrochloric acid, and and Ca content of the hydrochloric acid solution was determined by inductively coupled plasma atomic emission spectrometry (ICP-AES).
  • the abovementioned molding compositions F and comparative molding compounds VF were metered as granules under identical conditions into an injection molding machine, melted and injection molded in a tie-rod / weld-joint shape without degassing openings. Injection of the tension rod was carried out in this form from the two head sides, so that the two enamel fronts met in the middle of the mold and gave a weld line. After every 500 shots, ie injection-molded tensile bars, the mold was removed, the moldings occurring in the vicinity of the weld line visually assessed and assessed according to a scale of 1 (very good, no moldings) to 6 (poor, strong moldings).
  • Table 1* example molding compound Ca content of the molding compound [mg / kg] Mg content of the molding compound [mg / kg] Assessment of the formation of moldings V-1 VFC ⁇ 3 510 5 2 FD ⁇ 3 ⁇ 3 2 3 FE ⁇ 3 ⁇ 3 2 V-4 VFJ ⁇ 3 370 4-5 5 FK ⁇ 3 ⁇ 3 2 V-6 VFL ⁇ 3 360 4-5 7 FM ⁇ 3 ⁇ 3 2 V-8 VFN 11 135 3 9 FO 5 36 2-3 10 FP 8th ⁇ 3 2 V-11 VFQ ⁇ 3 212 4 * Examples and molding compounds preceded by "V-" are not inventive and are for comparison
  • the examples show that the inventive method for the production of molded parts by molding thermoplastic molding compositions F compared to the known methods exhibit a reduced deposit formation on the forming tool and / or the molding surface.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Injection Moulding Of Plastics Or The Like (AREA)
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Abstract

The invention relates to a method for producing molded parts by molding thermoplastic molding compounds F having reduced deposit formation, whereby according to the invention, the thermoplastic molding compounds comprise magnesium and/or calcium compounds in an amount from 0 mg/kg to 100 mg/kg (calculated as the sum of the mg Mg and the mg Ca per kg of thermoplastic molding compound F, and determined by means of atomic emission spectrometry using inductively coupled plasma (ICP-AES)); the invention further relates to the use of molding compounds F in the method according to the invention and molded parts that can be produced using the method according to the invention.

Description

Die Erfindung betrifft Verfahren zur Herstellung von Formteilen durch Formgebung thermoplastischer Formmassen F mit verringerter Belagsbildung am Formgebungswerkzeug.The invention relates to processes for the production of molded parts by molding thermoplastic molding compositions F with reduced deposit formation on the forming tool.

Außerdem betrifft die vorliegende Erfindung die Verwendung von Formmassen F in den erfindungsgemäßen Verfahren sowie Formteile, welche nach den erfindungsgemäßen Verfahren herstellbar sind.In addition, the present invention relates to the use of molding compositions F in the process of the invention and moldings which can be produced by the process according to the invention.

Im Stand der Technik sind die unterschiedlichsten thermoplastischen Formmassen sowie Verfahren zur Herstellung von Formteilen durch Formgebung dieser thermoplastischen Formmassen beschrieben. Bei diesen Formgebungsverfahren werden Kunststoffe aufgeschmolzen und durch Düsen beispielsweise in Formen oder auf Transportbänder gepresst. Ein oftmals auftretendes Problem bei diesen Formgebungsverfahren ist die Bildung von Formbelägen auf den Formgebungswerkzeugen, hier bevorzugt im Anguss- und im Entlüftungsbereich, und/oder auf den Formteiloberflächen. Die Beläge bestehen aus Ausscheidungen aus dem Kunststoff. Sie können z.B. von Verunreinigungen oder Hilfsstoffen aus dem Produktionsprozess herrühren oder von kunststoffüblichen Zusatzstoffen wie Flammschutz-, Gleitmittel oder Pigmenten. Diese Formbeläge können zu einer verschlechterten Oberflächenqualität der Formteile, Problemen beim Bedrucken oder Verkleben und einer schlechten Abformung von Kavitäten führen.In the prior art, the most diverse thermoplastic molding compositions and methods for the production of moldings by shaping these thermoplastic molding compositions are described. In these molding processes plastics are melted and pressed through nozzles, for example, in molds or on conveyor belts. An often occurring problem in these molding processes is the formation of moldings on the forming tools, preferably in the sprue and vent areas, and / or on the mold surfaces. The pads are made of plastic waste. You can e.g. from impurities or auxiliaries from the production process or from plastics-compatible additives such as flame retardants, lubricants or pigments. These moldings can lead to a deterioration in the surface quality of the molded parts, problems in printing or bonding and poor impression of cavities.

Die WO 98/28344 offenbart beispielsweise Verfahren zur Herstellung thermoplastischer Formmassen, bei denen Pfropfkautschukdispersionen nicht durch Zusatz von Säuren oder Salzen als Koagulantien sondern durch eine spezielle mechanische Scherfällung koaguliert werden. Dadurch werden Verunreinigungen in den thermoplastischen Formmassen, die zu einer Beeinträchtigung der Produkteigenschaften führen können, weitgehend vermieden. Die Gehalte etwaiger Salze, Säuren oder Verunreinigungen werden nicht offenbart. Ebensowenig werden Angaben zur Formteilherstellung aus diesen thermoplastischen Formmassen gemacht.The WO 98/28344 discloses, for example, processes for the preparation of thermoplastic molding compositions in which graft rubber dispersions are not coagulated by the addition of acids or salts as coagulants but by a special mechanical shear precipitation. As a result, impurities in the thermoplastic molding compositions, which can lead to an impairment of the product properties, largely avoided. The contents of any salts, acids or impurities are not disclosed. Information on the production of molded parts from these thermoplastic molding compounds is just as little made.

Die DE 44 08 213 A1 beschreibt ABS-Formmassen enthaltend 0,001 bis 0,3 Gew.-% spezieller Salze, darunter auch bestimmte Magnesium- und Calciumverbindungen. Die Verarbeitung dieser ABS-Formmassen bei höherer Temperatur zu einem Formteil soll mit verringerter Verfärbung und damit einer verbesserten Eigenfarbe der Polymere möglich sein. Weitere mögliche Schwierigkeiten bei der Formteilherstellung, insbesondere eine Verringerung der Formbelagsbildung, werden nicht diskutiert.The DE 44 08 213 A1 describes ABS molding compositions containing 0.001 to 0.3 wt .-% of special salts, including certain magnesium and calcium compounds. The processing of these ABS molding compositions at a higher temperature to form a molded article should be possible with reduced discoloration and thus an improved inherent color of the polymers. Further possible difficulties in the production of moldings, in particular a reduction in the formation of moldings, are not discussed.

Der in WO 02/42347 offenbarten Erfindung liegt die Aufgabe zugrunde, Formbeläge bei der Formteilherstellung zu verhindern. Die Lösung dieser Aufgabe besteht gemäß dieser Schrift im Zusatz eines pH-Puffersystems nach Beendigung der Polymerisation des kautschukelastischen Polymerisats. Die Mengenanteile etwaiger Magnesium- oder Calciumverbindungen in den dergestalt hergestellten thermoplastischen Formmassen werden nicht offenbart.The in WO 02/42347 disclosed invention is the object of preventing moldings in the production of molded parts. The solution to this problem is according to this document in the addition of a pH buffer system after completion of the polymerization of the elastomeric polymer. The proportions of any magnesium or calcium compounds in the thus prepared thermoplastic molding compositions are not disclosed.

Auch der in WO 01/48070 offenbarten Erfindung liegt die Aufgabe zugrunde, Formbeläge bei der Formteilherstellung zu minimieren bzw. verhindern. Die Lösung dieser Aufgabe besteht gemäß dieser Schrift im Zusatz von 0,02 bis 10 Gew.-% eines Magnesiumoxids (entsprechend 120 bis 60 000 mg/kg Mg), welches eine Zitronensäurezahl von < 1.500 sek aufweist, als Additiv bei der Formteilherstellung.Also the in WO 01/48070 DISCLOSURE OF THE INVENTION It is an object of the invention to minimize or prevent moldings in the production of molded parts. The solution to this problem is according to this document in the addition of 0.02 to 10 wt .-% of a magnesium oxide (corresponding to 120 to 60 000 mg / kg of Mg), which has a citric acid number of <1500 sec, as an additive in the molding production.

Gemäß der Lehre von EP 630 938 A1 weisen flammgeschützte thermoplastische Formmassen beim Spritzgießen zu Formteilen eine einheitliche Oberfläche ohne Verfärbungen, Ausblühungen und Ausgasung auf, wenn das eingesetzte Flammschutzmittel einen Magnesiumgehalt von 50 mg/kg oder weniger aufweist. Daß der Magnesiumgehalt der gesamten thermoplastischen Formmasse im Hinblick auf die Lösung der zugrunde liegenden Aufgabe eine Bedeutung haben könnte, ist der Schrift nirgends zu entnehmen.According to the doctrine of EP 630 938 A1 have flame-retardant thermoplastic molding compositions in injection molding to moldings a uniform surface without discoloration, efflorescence and outgassing, if the flame retardant used has a magnesium content of 50 mg / kg or less. That the magnesium content of the entire thermoplastic molding composition with regard to the solution of the underlying task could have a meaning, the Scripture is nowhere to be found.

Aufgabe der vorliegenden Erfindung war es, Verfahren zur Herstellung von Formteilen durch Formgebung thermoplastischer Formmassen bereit zu stellen, die gegenüber den bekannten Verfahren eine verringerte Belagsbildung am Formgebungswerkzeug und/oder der Formteiloberfläche aufweisen.The object of the present invention was to provide processes for the production of molded parts by shaping thermoplastic molding compositions which, compared to the known processes, have a reduced formation of deposits on the shaping tool and / or the molding surface.

Demgemäß wurden die eingangs definierten Verfahren gefunden, wobei erfindungswesentlich ist, daß die thermoplastischen Formmassen F Magnesium- und/oder Calciumverbindungen in einer Menge von 0 mg/kg bis 100 mg/kg (gerechnet als Summe der mg Mg und der mg Ca pro kg thermoplastischer Formmasse F und bestimmt mittels Atomemissionsspektrometrie mit induktiv gekoppeltem Plasma (ICP-AES)) enthalten.Accordingly, the method defined above were found, it being essential to the invention that the thermoplastic molding compositions F magnesium and / or calcium compounds in an amount of 0 mg / kg to 100 mg / kg (calculated as the sum of mg mg and mg Ca per kg of thermoplastic Molding composition F and determined by means of inductively coupled plasma atomic emission spectrometry (ICP-AES)).

Die erfindungsgemäßen Verfahren zur Herstellung von Formteilen durch Formgebung thermoplastischer Formmassen F weisen gegenüber den bekannten Verfahren eine verringerte Belagsbildung am Formgebungswerkzeug und/oder der Formteiloberfläche auf.The processes according to the invention for producing molded parts by molding thermoplastic molding compositions F have a reduced deposit formation on the forming tool and / or the molding surface compared to the known processes.

Die erfindungsgemäßen Verfahren sowie die weiteren erfindungsgemäßen Verwendungen und Gegenstände werden im folgenden beschrieben.The processes according to the invention and the other uses and articles according to the invention are described below.

Erfindungswesentlich ist, daß zur Herstellung der Formteile durch Formgebung thermoplastische Formmassen F als Einsatzstoff eingesetzt werden, die bis 75 mg/kg, insbesondere von 5 mg/kg bis 50 mg/kg (jeweils gerechnet als Summe der mg Mg und der mg Ca pro kg thermoplastischer Formmasse F) enthalten Die Magnesium- und Calciumgehalte der thermoplastischen Formmassen werden mit tels Atomemissionsspektrometrie mit induktiv gekoppeltem Plasma (ICP-AES) bestimmt werden; diese Methode ist dem Fachmann bekannt und in der Literatur beschrieben.It is essential to the invention that for the production of the molded parts by molding thermoplastic molding compositions F are used as the starting material, the up to 75 mg / kg, in particular from 5 mg / kg to 50 mg / kg (in each case calculated as the sum of mg mg and mg Ca per kg of thermoplastic molding material F) The magnesium and calcium contents of the thermoplastic molding compositions are inductive with atomic emission spectrometry coupled plasma (ICP-AES); this method is known to the person skilled in the art and described in the literature.

Bevorzugt einsetzbare Magnesium- und/oder Calciumverbindungen sind Magnesiumoxid, Magnesiumhydroxid, Magnesiumsulfat, Magnesiumcarbonat, Magnesiumstearat, Calciumhydroxid, Calciumcarbonat, Calciumsulfat, Calciumstearat oder Mischungen aus zwei oder mehr der genannten Verbindungen. Besonders bevorzugt sind Magnesiumsulfat und Magnesiumstearat.Preferred magnesium and / or calcium compounds are magnesium oxide, magnesium hydroxide, magnesium sulfate, magnesium carbonate, magnesium stearate, calcium hydroxide, calcium carbonate, calcium sulfate, calcium stearate or mixtures of two or more of the compounds mentioned. Particularly preferred are magnesium sulfate and magnesium stearate.

Die thermoplastischen Formmassen F können als Kunststoffkomponente grundsätzlich alle dem Fachmann bekannten und in der Literatur beschriebenen thermoplastischen Polymere enthalten; auch Mischungen aus mehreren dieser thermoplastischen Polymere sind geeignet.As thermoplastic components, the thermoplastic molding compositions F can in principle contain all thermoplastic polymers known to the person skilled in the art and described in the literature; also mixtures of several of these thermoplastic polymers are suitable.

Geeignete thermoplastische Polymere sind z.B.:

  • Polyolefine wie Polyethylen und Polypropylen,
  • Polyvinylchlorid,
  • Styrolpolymere wie Polystyrol (schlagfest oder nicht schlagfest modifiziert),
  • schlagzähmodifizierte vinylaromatische Copolymere wie ABS (Acrylnitril-Butadien-Styrol), ASA (Acrylnitril-Styrol-Acrylat) und MABS (transparentes ABS, enthaltend Methacrylat-Einheiten),
  • Styrol-Butadien-Blockcopolymere ("SBC"), insbesondere thermoplastische Elastomere auf Basis von Styrol ("S-TPE"),
  • Polyamide,
  • Polyester wie Polyethylenterephthalat (PET), Polyethylenterephthalat-Glycol (PETG) und Polybutylenterephthalat (PBT),
  • Polycarbonat (z.B. Makrolon® der Bayer AG),
  • Polymethylmethacrylat (PMMA),
  • Poly(ether)sulfone und
  • Polyphenylenoxid (PPO).
Suitable thermoplastic polymers are, for example:
  • Polyolefins such as polyethylene and polypropylene,
  • polyvinyl chloride,
  • Styrene polymers such as polystyrene (impact-resistant or not impact-modified),
  • impact-modified vinyl aromatic copolymers such as ABS (acrylonitrile-butadiene-styrene), ASA (acrylonitrile-styrene-acrylate) and MABS (transparent ABS containing methacrylate units),
  • Styrene-butadiene block copolymers ("SBC"), in particular styrene-based thermoplastic elastomers ("S-TPE"),
  • polyamides,
  • Polyesters such as polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG) and polybutylene terephthalate (PBT),
  • Polycarbonate (eg Makrolon ® from Bayer AG),
  • Polymethyl methacrylate (PMMA),
  • Poly (ether) sulfones and
  • Polyphenylene oxide (PPO).

Als Kunststoffkomponente der thermoplastischen Formmassen F bevorzugt einsetzbare thermoplastische Polymere sind ein oder mehrere Polymere ausgewählt aus der Gruppe ASA, ABS, Polyamide und Polyester.As the plastic component of the thermoplastic molding compositions F preferably usable thermoplastic polymers are one or more polymers selected from the group ASA, ABS, polyamides and polyesters.

Bevorzugte schlagzäh modifizierte vinylaromatische Copolymere sind schlagzäh modifizierte Copolymerisate aus vinylaromatischen Monomeren und Vinylcyaniden (SAN). Bevorzugt werden als schlagzähmodifiziertes SAN ASA-Polymerisate und/oder ABS-Polymerisate eingesetzt, sowie (Meth)acrylat-Acrylnitril-Butadien-Styrol-Polymerisate ("MABS", transparentes ABS), aber auch Blends von SAN, ABS, ASA und MABS mit anderen Thermoplasten wie Polycarbonat, Polyamid, Polyethylenterephthalat, Polybutylenterephthalat, PVC, Polyolefinen.
Unter ASA-Polymerisaten werden im allgemeinen schlagzähmodifizierte SAN-Polymerisate verstanden, bei denen kautschukelastische Pfropfcopolymerisate von vinylaromatischen Verbindungen, insbesondere Styrol, und Vinylcyaniden, insbesondere Acrylnitril, auf Polyalkylacrylatkautschuken in einer Copolymermatrix aus insbesondere Styrol und/oder α-Methylstyrol und Acrylnitril vorliegen. ASA-Polymerisate sind dem Fachmann bekannt und in der Literatur beschriebenen, beispielsweise in DIN EN ISO 6402-1 DE vom Februar 2003.
Unter ABS-Polymerisaten werden im allgemeinen schlagzähmodifizierte SAN-Polymerisate verstanden, bei denen Dien-Polymerisate, insbesondere 1,3-Polybutadien, in einer Copolymermatrix aus insbesondere Styrol und/oder α-Methylstyrol und Acrylnitril vorliegen. ABS-Polymerisate sind dem Fachmann bekannt und in der Literatur beschriebenen, beispielsweise in DIN EN ISO 2580-1 DE vom Februar 2003.Preferred impact-modified vinylaromatic copolymers are impact-modified copolymers of vinylaromatic monomers and vinyl cyanides (SAN). ASA polymers and / or ABS polymers are preferably used as the impact-modified SAN, as well as (meth) acrylate-acrylonitrile-butadiene-styrene polymers ("MABS", transparent ABS), but also blends of SAN, ABS, ASA and MABS other thermoplastics such as polycarbonate, polyamide, polyethylene terephthalate, polybutylene terephthalate, PVC, polyolefins.
ASA polymers are generally understood to be impact-modified SAN polymers in which rubber-elastic graft copolymers of vinylaromatic compounds, in particular styrene, and vinyl cyanides, in particular acrylonitrile, are present on polyalkyl acrylate rubbers in a copolymer matrix of, in particular, styrene and / or .alpha.-methylstyrene and acrylonitrile. ASA polymers are known to the person skilled in the art and described in the literature, for example in DIN EN ISO 6402-1 DE of February 2003.
ABS polymers are generally understood to be impact-modified SAN polymers in which diene polymers, in particular 1,3-polybutadiene, are present in a copolymer matrix of, in particular, styrene and / or α-methylstyrene and acrylonitrile. ABS polymers are known to the person skilled in the art and described in the literature, for example in DIN EN ISO 2580-1 DE of February 2003.

Als Kunststoffkomponente der thermoplastischen Formmassen F außerdem bevorzugt einsetzbare thermoplastische Polymere sind teilkristalline Polyolefine, wie Homo- oder Copolymerisate von Ethylen, Propylen, Buten-1, Penten-1, Hexen-1, 4-Methyl-penten-1 sowie Ethylencopolymerisate mit Vinylacetat, Vinylalkohol, Ethylacrylat, Butyl-acrylat oder Methacrylat. Bevorzugt wird ein High-Density-Polyethylen (HDPE), Low-Density-Polyethylen (LDPE), Linear-Low-Density-Polyethylen (LLDPE), Polypropylen (PP), Ethylen-Vinylacetat-Copolymerisat (EVA) oder Ethylen-Acryl-Copolymerisat eingesetzt. Insbesondere bevorzugt ist Polypropylen.As a plastic component of the thermoplastic molding compositions F also preferably usable thermoplastic polymers are partially crystalline polyolefins such as homopolymers or copolymers of ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methyl-1-penten-1 and ethylene copolymers with vinyl acetate, vinyl alcohol , Ethyl acrylate, butyl acrylate or methacrylate. Preference is given to a high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA) or ethylene-acrylic Copolymer used. Particularly preferred is polypropylene.

Als Kunststoffkomponente der thermoplastischen Formmassen F ebenfalls bevorzugt einsetzbare thermoplastische Polymere sind Polycarbonate. Die Polycarbonate haben vorzugsweise ein Molekulargewicht (Gewichtsmittelwert Mw, bestimmt mittels Gelpermeationschromatographie in Tetrahydrofuran gegen Polystyrolstandards) im Bereich von 10 000 bis 60 000 g/mol. Sie sind z.B. entsprechend den Verfahren der DE-B-1 300 266 durch Grenzflächenpolykondensation oder gemäß dem Verfahren der DE-A-1 495 730 durch Umsetzung von Diphenylcarbonat mit Bisphenolen erhältlich. Bervorzugtes Bisphenol ist 2,2-Di(4-hydroxyphenyl)propan, im allgemeinen - wie auch im folgenden - als Bisphenol A bezeichnet.
Anstelle von Bisphenol A können auch andere aromatische Dihydroxyverbindungen verwendet werden, insbesondere 2,2-Di(4-hydroxyphenyl)pentan, 2,6-Dihydroxynaphthalin, 4,4'-Dihydroxydiphenylsulfan, 4,4'-Dihydroxydiphenylether, 4,4'-Dihydroxydiphenylsulfit, 4,4'-Dihydroxydiphenylmethan, 1,1-Di-(4-hydroxyphenyl)ethan, 4,4-Dihydroxydiphenyl oder Dihydroxydiphenylcycloalkane, bevorzugt Dihydroxydiphenylcyclohexane oder Dihydroxylcyclopentane, insbesondere 1,1-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan sowie Mischungen der vorgenannten Dihydroxyverbindungen.
Besonders bevorzugte Polycarbonate sind solche auf der Basis von Bisphenol A oder Bisphenol A zusammen mit bis zu 80 Mol-% der vorstehend genannten aromatischen Dihydroxyverbindungen.
Besonders gut geeignete Polycarbonate sind solche, die Einheiten enthalten, welche sich von Resorcinol- oder Alkylresorcinolestern ableiten, wie sie beispielsweise in WO 00/61664 , WO 00/15718 oder WO 00/26274 beschrieben werden; solche Polycarbonate werden beispielsweise von General Electric Company unter der Marke SollX® vertrieben.
Es können auch Copolycarbonate gemäß der US-A 3 737 409 verwendet werden; von besonderem Interesse sind dabei Copolycarbonate auf der Basis von Bisphenol A und Di-(3,5-dimethyl-dihydroxyphenyl)sulfon, die sich durch eine hohe Wärmeformbeständigkeit auszeichnen. Ferner ist es möglich, Mischungen unterschiedlicher Polycarbonate einzusetzen.Also preferably used as a plastic component of the thermoplastic molding compositions F thermoplastic polymers are polycarbonates. The polycarbonates preferably have a molecular weight (weight average M w , as determined by gel permeation chromatography in tetrahydrofuran against polystyrene standards) in the range of 10,000 to 60,000 g / mol. They are eg according to the procedures of DE-B-1 300 266 by interfacial polycondensation or according to the method of DE-A-1 495 730 by reaction of diphenyl carbonate with bisphenols available. Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, generally referred to as bisphenol A, as hereinafter.
Instead of bisphenol A, it is also possible to use other aromatic dihydroxy compounds, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxyniphenyl ether. Dihydroxydiphenylsulfite, 4,4'-dihydroxydiphenylmethane, 1,1-di- (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl or dihydroxydiphenylcycloalkanes, preferably dihydroxydiphenylcyclohexanes or dihydroxyclopentanes, especially 1,1-bis (4-hydroxyphenyl) -3,3 , 5-trimethylcyclohexane and mixtures of the aforementioned dihydroxy compounds.
Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mol% of the abovementioned aromatic dihydroxy compounds.
Particularly suitable polycarbonates are those which contain units which are derived from resorcinol or Alkylresorcinolestern, as for example in WO 00/61664 . WO 00/15718 or WO 00/26274 to be discribed; These polycarbonates are marketed, for example, General Electric Company under the trademark SollX ®.
Copolycarbonates according to the US-A 3,737,409 be used; Of particular interest are copolycarbonates based on bisphenol A and di- (3,5-dimethyl-dihydroxyphenyl) sulfone, which are characterized by a high heat resistance. It is also possible to use mixtures of different polycarbonates.

Bevorzugt ist in den thermoplastischen Formmassen F als thermoplastisches Polymer jedes aromatische oder aliphatische thermoplastische Polyurethan geeignet, bevorzugt sind amorphe aliphatische thermoplastische Polyurethane geeignet, die transparent sind. Aliphatische thermoplastische Polyurethane und deren Herstellung sind dem Fachmann bekannt, beispielsweise aus EP-B1 567 883 oder DE-A 10321081 , und kommerziell verfügbar, beispielsweise unter den Marken Texin® und Desmopan® der Bayer Aktiengesellschaft.In the thermoplastic molding compositions F, any aromatic or aliphatic thermoplastic polyurethane is preferably suitable as the thermoplastic polymer, preferably amorphous aliphatic thermoplastic polyurethanes which are transparent are suitable. Aliphatic thermoplastic polyurethanes and their preparation are known in the art, for example from EP-B1 567 883 or DE-A 10321081 , And commercially available, for example under the brand names Texin ® and Desmopan ® Bayer Aktiengesellschaft.

Die thermoplastischen Formmassen F können alle dem Fachmann bekannten und in der Literatur beschriebenen kunststoffüblichen Zusatzstoffe enthalten. Bevorzugt enthalten diese kunststoffüblichen Zusatzstoffe im Wesentlichen keine Magnesium-und/oder Calciumverbindungen. Der Begriff "im Wesentlichen keine" bedeutet, dass der Gehalt an Magnesium-und/oder Calciumverbindungen in den kunststoffüblichen Zusatzstoffen unterhalb der Nachweisgrenze der ICP-AES-Analysemethode liegt.The thermoplastic molding compositions F may contain all known in the art and described in the literature kunststofpfblichen additives. These plastic-compatible additives preferably contain substantially no magnesium and / or calcium compounds. The term "essentially none" means that the content of magnesium and / or calcium compounds in the plastic-compatible additives is below the detection limit of the ICP-AES analysis method.

Kunststoffübliche Zusatzstoffe im Sinne der vorliegenden Erfindung sind beispielsweise Stabilisatoren und Oxidationsverzögerer, Mittel gegen Wärmezersetzung und Zersetzung durch ultraviolettes Licht, Gleit- und Entformungsmittel, Farbstoffe und Pigmente und Weichmacher sowie Fasern, beispielsweise Glasfasern oder Kohlenstofffasern.Plastic additives for the purposes of the present invention are, for example, stabilizers and antioxidants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, dyes and pigments and plasticizers and fibers, for example glass fibers or carbon fibers.

Oxidationsverzögerer und Wärmestabilisatoren, die der thermoplastischen Formmasse F gemäß der Erfindung zugesetzt werden können, sind z. B. Halogenide von Metallen der Gruppe I des Periodensystems, z. B. Natrium-, Kalium-, Lithium-Halogenide. Weiterhin können Zinkfluorid und Zinkchlorid verwendet werden. Ferner sind sterisch gehinderte Phenole, Hydrochinone, substituierte Vertreter dieser Gruppe, sekundäre aromatische Amine, gegebenenfalls in Verbindung mit phosphorhaltigen Säuren bzw. deren Salze, und Mischungen dieser Verbindungen, vorzugsweise in Konzentrationen bis zu 1 Gew.-%, bezogen auf das Gewicht der thermoplastischen Formmassen F, einsetzbar.Oxidation retarders and heat stabilizers that can be added to the thermoplastic molding material F according to the invention are, for. B. halides of metals of Group I of the Periodic Table, z. For example, sodium, potassium, lithium halides. Furthermore, zinc fluoride and zinc chloride can be used. Further, sterically hindered phenols, hydroquinones, substituted members of this group, secondary aromatic amines, optionally in conjunction with phosphorus-containing acids or their salts, and mixtures of these compounds, preferably in concentrations up to 1 wt .-%, based on the weight of the thermoplastic Molding compounds F, can be used.

Beispiele für UV-Stabilisatoren sind verschiedene substituierte Resorcine, Salicylate, Benzotriazole und Benzophenone, die im Allgemeinen in Mengen bis zu 2 Gew.-%, bezogen auf das Gewicht der thermoplastischen Formmassen F, eingesetzt werden.Examples of UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benzophenones, which are generally used in amounts of up to 2% by weight, based on the weight of the thermoplastic molding compositions F.

Gleit- und Entformungsmittel, die in der Regel in Mengen bis zu 1 Gew.-%, bezogen auf das Gewicht der thermoplastischen Formmassen F, zugesetzt werden können, sind Stearinsäure, Stearylalkohol, Stearinsäurealkylester und -amide sowie Ester des Pentaerythrits mit langkettigen Fettsäuren. Es können auch Salze des Zinks oder Aluminiums der Stearinsäure sowie Dialkylketone, z. B. Distearylketon, eingesetzt werden. Erfindungsgemäß geeignet sind insbesondere Stearate sowie N,N'-Ethylen-bisstearamid.Lubricants and mold release agents, which can generally be added in amounts of up to 1% by weight, based on the weight of the thermoplastic molding compositions F, of stearic acid, stearyl alcohol, stearic acid alkyl esters and amides and esters of pentaerythritol with long-chain fatty acids. There may also be salts of zinc or aluminum of stearic acid and dialkyl ketones, for. B. distearyl ketone used. Particularly suitable according to the invention are stearates and also N, N'-ethylene-bisstearamide.

Als Glasfasern können in den erfindungsgemäßen Formmassen F alle dem Fachmann bekannten und in der Literatur beschriebenen Glasfasern eingesetzt werden (siehe beispielsweise Milewski, J.V., Katz, H.S. "Handbook of Reinforcements for Plastics", S. 233 ff., Van Nostrand Reinholt Company Inc, 1987 ).As glass fibers, it is possible in the molding compositions F according to the invention to use all glass fibers known to the person skilled in the art and described in the literature (see, for example, US Pat Milewski, JV, Katz, HS "Handbook of Reinforcements for Plastics", p. 233 et seq., Van Nostrand Reinholt Company Inc, 1987 ).

In den erfindungsgemäßen Verfahren besonders bevorzugt einsetzbare thermoplastischen Formmassen F enthalten neben der mindestens einen Magnesium- und/oder Calciumverbindung

  1. A) 20 bis 100 Gew.-%, bevorzugt 30 bis 100 Gew.-%, besonders bevorzugt 40 bis 100 Gew.-%, mindestens eines schlagzähmodifizierten vinylaromatischen Copolymers ausgewählt aus der Gruppe Acrylnitril-Butadien-Styrol-Copolymere (ABS), Acrylnitril-Styrol-Acrylat-Copolymere (ASA) und Methacrylat-Acrylnitril-Butadien-Styrol-Copolymere (MABS),
  2. B) 0 bis 80 Gew.-%, bevorzugt 0 bis 70 Gew.-%, besonders bevorzugt 0 bis 60 Gew.-%, mindestens eines Polycarbonats (PC) und
  3. C) 0 bis 60 Gew.-%, bevorzugt 0 bis 45 Gew.-%, besonders bevorzugt 0 bis 25 Gew.-%, weiterer kunststoffüblicher Zusatzstoffe enthalten,
wobei die Gewichtsprozente jeweils auf das Gesamtgewicht der Komponenten A) bis C) bezogen sind und zusammen 100 Gew.-% ergeben.In the process according to the invention particularly preferably usable thermoplastic molding compositions F contain in addition to the at least one magnesium and / or calcium compound
  1. A) 20 to 100 wt .-%, preferably 30 to 100 wt .-%, particularly preferably 40 to 100 wt .-%, of at least one impact-modified vinyl aromatic copolymer selected from the group of acrylonitrile-butadiene-styrene copolymers (ABS), acrylonitrile Styrene-acrylate copolymers (ASA) and methacrylate-acrylonitrile-butadiene-styrene copolymers (MABS),
  2. B) 0 to 80 wt .-%, preferably 0 to 70 wt .-%, particularly preferably 0 to 60 wt .-%, of at least one polycarbonate (PC) and
  3. C) 0 to 60 wt .-%, preferably 0 to 45 wt .-%, particularly preferably 0 to 25 wt .-%, further Kunststofpfblicher additives contain,
wherein the weight percentages are based in each case on the total weight of components A) to C) and together give 100% by weight.

Die thermoplastischen Formmassen F können nach dem Fachmann bekannten und in der Literatur beschriebenen Verfahren, insbesondere durch Schmelzevermischung der thermoplastischen Polymere, der Magnesium- und/oder Calciumverbindung und ggf. der kunststoffüblichen Zusatzstoffe in einem Schneckenextruder, hergestellt werden.The thermoplastic molding compositions F can be prepared by processes known to the person skilled in the art and described in the literature, in particular by melt-mixing of the thermoplastic polymers, the magnesium and / or calcium compound and optionally the plastic-compatible additives in a screw extruder.

Als Schneckenextruder können Einschneckenextruder oder Doppelschneckenextruder, die gleichsinnig drehend und ineinandergreifend, als auch gegenläufig kämmend sowie nicht kämmend sein können, verwendet werden. Bevorzugt werden Doppelschneckenextruder eingesetzt. Besonders bevorzugt sind gleichsinnig drehende, kämmende Doppelschneckenextruder. Geeignete Schneckenextruder sind beispielsweise in Saechtling, Kunststoff-Taschenbuch, Hanser Verlag, München, Wien, Ausgabe 26, 1995, Seiten 191 bis 246 , beschrieben.As screw extruders, single-screw extruders or twin-screw extruders, which can be rotating and intermeshing in the same direction, as well as counter-intermeshing and non-combing, can be used. Preference is given to using twin-screw extruders. Particularly preferred are co-rotating, intermeshing twin-screw extruders. Suitable screw extruders are, for example, in Saechtling, Plastic Paperback, Hanser Verlag, Munich, Vienna, Issue 26, 1995, pages 191-246 , described.

Bei den erfindungsgemäßen Verfahren zur Herstellung von Formteilen durch Formgebung thermoplastischer Formmassen F erfolgt die Formgebung bevorzugt durch Extrusion, insbesondere Extrusion zu Granulat, Folien, Platten, Strängen oder Profilen, oder durch Spritzguß zu Formkörpern; besonders bevorzugt ist der Spritzguß zu Formkörpern. Die genannten Verfahren der Extrusion und des Spritzguß sowie die dabei verwendeten Vorrichtungen sind als solche dem Fachmann bekannt und in der Literatur beschrieben.In the method according to the invention for the production of molded parts by molding thermoplastic molding compositions F, the molding is preferably carried out by extrusion, in particular extrusion into granules, films, sheets, strands or profiles, or by injection molding into moldings; Particularly preferred is the injection molding into moldings. The methods of extrusion and injection molding mentioned and the devices used are known as such to the person skilled in the art and described in the literature.

Durch den Einsatz der thermoplastischen Formmassen F enthaltend Magnesium-und/oder Calciumverbindungen in der oben genannten Menge bei den erfindungsgemäßen Verfahren wird gegenüber den bekannten Verfahren zur Formgebung eine verringerte Belagsbildung am Formgebungswerkzeug erreicht.The use of the thermoplastic molding compositions F containing magnesium and / or calcium compounds in the abovementioned amount in the processes according to the invention achieves a reduced formation of deposits on the shaping tool compared to the known methods of shaping.

Besonders bevorzugte Formteile, die sich nach den erfindungsgemäßen Verfahren herstellen lassen, sind beispielsweise Haushaltsartikel, elektronische Bauteile, medizinische Geräte, Kfz-Bauteile und Baumaterialien, insbesondere spritzgegossene Chipkarten und Spielbausteine, Gehäuse für elektrische und elektronische Teile, beispielsweise Küchenmaschinen, Rasierapparate, Telephone, Staubsauger, Monitorgehäuse, Tastaturen, Elektro-Rasenmäher, Spielzeugeisenbahnen, Waschmaschinen, Geschirrspüler, Kühlschränke, Teile für den Innenraum von Kraftfahrzeugen, und für den Außeneinsatz an Kraftfahrzeugen, beispielsweise Radkappen, Außenspiegel (eingefärbt, lackiert oder galvanisiert), Kühlergrills und Spoiler.Particularly preferred molded parts which can be produced by the process according to the invention are, for example, household articles, electronic components, medical devices, automotive components and building materials, in particular injection-molded chip cards and toy building blocks, housings for electrical and electronic parts, for example food processors, razors, telephones, vacuum cleaners Monitor enclosures, keyboards, electric lawn mowers, toy trains, washing machines, dishwashers, refrigerators, automotive interior parts, and automotive exterior applications such as hubcaps, exterior mirrors (colored, painted or galvanized), grills and spoilers.

Die nach den erfindungsgemäßen Verfahren herstellbaren Formteile weisen durch die verringerte Belagsbildung bei der Formgebung eine -gegenüber nach bekannten Verfahren herstellbaren Formteilen- eine verbesserte Oberflächenqualität auf.The moldings which can be produced by the process according to the invention have an improved surface quality as a result of the reduced deposit formation during shaping compared to moldings which can be produced by known processes.

Die Erfindung wird nachstehend anhand von Beispielen näher erläutert.The invention will be explained in more detail below with reference to examples.

Beispiele:Examples:

Beispiele mit vorangestelltem "V-" sind nicht erfindungsgemäß und dienen zum Vergleich.Examples preceded by "V-" are not inventive and are for comparison.

Einsatzstoffe, Formmassen F und Vergleichsformmassen V-F, sowie deren Herstellung:Starting materials, molding compounds F and comparative molding compounds V-F, and their preparation:

Formmassen mit vorangestelltem "V-" sind nicht erfindungsgemäß und dienen zum Vergleich.Molding compounds preceded by "V-" are not inventive and are for comparison.

Herstellung von Pfropfkautschuken:Production of graft rubbers: Herstellung eines Butadien-Pfropfkautschuks A:Preparation of Butadiene Grafting Rubber A:

In einer Lösung von 0,6 Gew.-Teilen tert.-Dodecylmercaptan, 0,7 Gew.-Teilen Kaliumstearat als Emulgator, 0,2 Gew.-Teilen Kaliumperoxodisulfat und 0,2 Gew.-Teilen Natriumhydrogencarbonat in 80 Gew.-Teilen Wasser wurden bei 65°C 60 Gew.-Teile Butadien bis zu einem Monomerenumsatz von 98 Gew.-% polymerisiert. Der erhaltene Latex wurde durch Zusatz von 2,5 Gew.-Teilen einer 10 gew.-%-igen Emulsion eines Copolymeren aus 96 Gew.-% Ethylacrylat und 4 Gew.-% Methacrylamid agglomeriert. Zur so erhaltenen Dispersion wurden 40 Gew.-Teile Wasser, 0,4 Gew.-Teile Kaliumstearat und 0,2 Gew.-Teile Kaliumperoxodisulfat gegeben. Anschließend wurden 40 Gew.-Teile einer Mischung von 70 Gew.-% Styrol und 30 Gew.-% Acrylnitril innerhalb von 4 Stunden zugegeben und der Ansatz unter Rühren bei 70°C gehalten. Nach Beendigung der Pfropfmischpolymerisation wurde der Butadien-Pfropfkautschuk mittels Magnesiumsulfatlösung bei 89°C aus der Dispersion gefällt und im warmen Luftstrom getrocknet.In a solution of 0.6 parts by weight of tert-dodecyl mercaptan, 0.7 parts by weight of potassium stearate as emulsifier, 0.2 parts by weight of potassium peroxodisulfate and 0.2 parts by weight of sodium bicarbonate in 80 parts by weight Water was polymerized at 65 ° C 60 parts by weight of butadiene to a monomer conversion of 98 wt .-%. The resulting latex was agglomerated by adding 2.5 parts by weight of a 10% by weight emulsion of a copolymer of 96% by weight of ethyl acrylate and 4% by weight of methacrylamide. To the dispersion thus obtained were added 40 parts by weight of water, 0.4 parts by weight of potassium stearate and 0.2 parts by weight of potassium peroxodisulfate. Subsequently, 40 parts by weight of a mixture of 70 wt .-% of styrene and 30 wt .-% acrylonitrile were added within 4 hours and the mixture was kept under stirring at 70 ° C. After completion of the graft copolymerization of the butadiene graft rubber was precipitated by means of magnesium sulfate solution at 89 ° C from the dispersion and dried in a stream of warm air.

Herstellung eines Butadien-Pfropfkautschuks B:Preparation of Butadiene Graft Rubber B:

Die Herstellung des Butadien-Pfropfkautschuks B erfolgte bis zur Beendigung der Pfropfmischpolymerisation wie bei der Herstellung des Butadien-Pfropfkautschuks A beschrieben. Die anschließende Fällung des Butadien-Pfropfkautschuks B aus der Dispersion erfolgte jedoch nicht mittels Magnesiumsulfatlösung sondern durch Gefrierfällung auf einer Scherbeneismaschine, anschließender 30-minütiger Sinterung bei 121 °C und darauf folgende Abkühlung auf 60°C. Anschließend wurde Wasser auf einer Schleuder abgeschleudert. Der derart vorentwässerte Butadien-Pfropfkautschuk (Restfeuchtegehalt ca. 30 Gew.-%) wurde abschließend im warmen Luftstrom getrocknet.The preparation of the butadiene graft rubber B was carried out until completion of the graft copolymerization as described in the preparation of the butadiene graft rubber A. However, the subsequent precipitation of the butadiene graft rubber B from the dispersion was not carried out by means of magnesium sulfate solution but by freeze precipitation on a flake ice machine, followed by sintering for 30 minutes 121 ° C and subsequent cooling to 60 ° C. Subsequently, water was spun on a sling. The thus pre-dehydrated butadiene graft rubber (residual moisture content about 30 wt .-%) was finally dried in a stream of warm air.

Herstellung eines Acrylat-Pfropfkautschuks H:Preparation of an acrylate graft rubber H:

17,5 Gew.-Teile Butylacrylat und 0,1 Gew.-Teil Allylmethacrylat wurden in 150 Gew.-Teilen Wasser unter Zusatz von 0,2 Gew.-Teilen Kaliumstearat, 0,3 Gew.-Teilen Kaliumpersulfat, 0,3 Gew.-Teile Natriumhydrogencarbonat und 0,15 Gew.-Teilen Natriumpyrophosphat unter Rühren auf 60°C erwärmt. 10 Minuten nach dem Anspringen der Polymerisationsreaktion wurden innerhalb von 3 Stunden eine Mischung aus 82 Gew.-Teilen Butylacrylat und 0,4 Gew.-Teile Allylmethacrylat zugegeben. Nach Beendigung der Monomerzugabe wurde noch eine Stunde nachpolymerisiert. Zu einer Vorlage aus 2,5 Gew.-Teilen des so erhaltenen Kautschuklatex wurden nach Zugabe von 50 Gew.-Teilen Wasser und 0,1 Gew.-Teilen Kaliumperoxodisulfat im Verlauf von 3 Stunden gleichzeitig und separiert voneinander sowohl eine Mischung aus 49 Gew.-Teilen Butylacrylat und 0,25 Gew.-Teilen Allylmethacrylat, als auch eine Lösung von 0,5 Gew.-Teilen Kaliumstearat in 25 Gew.-Teilen Wasser bei 60°C zudosiert. Nach Dosierende wurde 2 Stunden nachpolymerisiert. 150 Gew.-Teile des so erhaltenen Kautschuklatex wurden mit 20 Gew.-Teilen Styrol und 60 Gew.-Teilen Wasser gemischt und unter Rühren nach Zusatz von weiteren 0,03 Gew.-Teilen Kaliumperoxodisulfat und 0,05 Gew.-Teiten Lauroylperoxid 3 Stunden auf 65°C erhitzt. Diese Pfropfmischpolymerisatdispersion wurde ohne weitere Zusatzstoffe mit 20 Gew.-Teilen einer Mischung aus Styrol und Acrylnitril (Gew.-Verhältnis 75:25) weitere 3 Stunden polymerisiert. Nach Beendigung der Pfropfmischpolymerisation wurde der Acrylat-Pfropfkautschuk mittels Magnesiumsulfatlösung bei 91°C aus der Dispersion gefällt und im warmen Luftstrom getrocknet.17.5 parts by weight of butyl acrylate and 0.1 part by weight of allyl methacrylate were dissolved in 150 parts by weight of water with the addition of 0.2 parts by weight of potassium stearate, 0.3 parts by weight of potassium persulfate, 0.3 wt Sodium bicarbonate and 0.15 parts by weight of sodium pyrophosphate with stirring to 60 ° C heated. 10 minutes after the initiation of the polymerization reaction, a mixture of 82 parts by weight of butyl acrylate and 0.4 part by weight of allyl methacrylate was added within 3 hours. After completion of the monomer addition was postpolymerized for one hour. To a template of 2.5 parts by weight of the rubber latex thus obtained were added after addition of 50 parts by weight of water and 0.1 parts by weight of potassium peroxodisulfate in the course of 3 hours simultaneously and separated from each other both a mixture of 49 wt. Butyl acrylate and 0.25 parts by weight of allyl methacrylate, as well as a solution of 0.5 parts by weight of potassium stearate in 25 parts by weight of water at 60 ° C added. After dosing, polymerization was continued for 2 hours. 150 parts by weight of the resulting rubber latex were mixed with 20 parts by weight of styrene and 60 parts by weight of water and with stirring after addition of another 0.03 parts by weight of potassium peroxodisulfate and 0.05 parts by weight of lauroyl peroxide Heated to 65 ° C for hours. This graft copolymer dispersion was polymerized without further additives with 20 parts by weight of a mixture of styrene and acrylonitrile (weight ratio 75:25) for a further 3 hours. After completion of the graft copolymerization of the acrylate graft rubber was precipitated by means of magnesium sulfate solution at 91 ° C from the dispersion and dried in a stream of warm air.

Herstellung eines Acrylat-Pfropfkautschuks I:Preparation of an acrylate graft rubber I:

Die Herstellung des Acrylat-Pfropfkautschuks I erfolgte bis zur Beendigung der Pfropfmischpolymerisation wie bei der Herstellung des Acrylat-Pfropfkautschuks H beschrieben. Die anschließende Fällung des Acrylat-Pfropfkautschuks I aus der Dispersion erfolgte jedoch nicht mittels Magnesiumsulfatlösung sondern durch Gefrierfällung auf einer Scherbeneismaschine, anschließender 30-minütiger Sinterung bei 121°C und darauf folgende Abkühlung auf 60°C. Anschließend wurde Wasser auf einer Schleuder abgeschleudert. Der derart vorentwässerte Acrylat-Pfropfkautschuk (Restfeuchtegehalt ca. 30 Gew.-%) wurde abschließend im warmen Luftstrom getrocknet.The preparation of the acrylate graft rubber I was carried out until completion of the graft copolymerization as described in the preparation of the acrylate graft rubber H. However, the subsequent precipitation of the acrylate graft rubber I from the dispersion was not carried out by means of magnesium sulfate solution but by freeze precipitation on a flake ice machine, followed by sintering at 121 ° C. for 30 minutes and subsequent cooling to 60 ° C. Subsequently, water was spun on a sling. The pre-dehydrated acrylate graft rubber (residual moisture content about 30% by weight) was finally dried in a stream of warm air.

Herstellung von Formmassen F und Vergleichsformmassen V-F:Production of molding compounds F and comparative molding compounds V-F: Herstellung von Vergleichsformmasse V-F-C (ABS):Preparation of comparative molding compound V-F-C (ABS):

48 Gew.-Teile des getrockneten Butadien-Pfropfkautschuks A wurden mit 52 Gew.-Teilen eines Granulats eines handelsüblichen Styrol-Acrylnitril-Copolymers mit einem Acrylnitrilgehalt von 24 Gew.-% und einer Viskositätszahl von 64 bei 250°C auf einem Zweiwellenextruder ZSK 30 extrudiert und granuliert. Der Gehalt an Magnesium im Granulat betrug 510 mg/kg, der Gehalt an Calcium im Granulat betrug < 3 mg/kg.48 parts by weight of the dried butadiene graft rubber A were mixed with 52 parts by weight of granules of a commercially available styrene-acrylonitrile copolymer having an acrylonitrile content of 24 wt .-% and a viscosity of 64 at 250 ° C on a ZSK 30 twin-screw extruder extruded and granulated. The content of magnesium in the granules was 510 mg / kg, the content of calcium in the granules was <3 mg / kg.

Herstellung von Formmasse F-D (ABS):Production of molding compound F-D (ABS):

48 Gew.-Teile des getrockneten Butadien-Pfropfkautschuks B wurden mit 52 Gew.-Teilen eines Granulats eines handelsüblichen Styrol-Acrylnitril-Copolymers mit einem Acrylnitrilgehalt von 24 Gew.-% und einer Viskositätszahl von 64 bei 250°C auf einem Zweiwellenextruder ZSK 30 extrudiert und granuliert. Der Gehalt an Magnesium im Granulat betrug < 3 mg/kg, der Gehalt an Calcium im Granulat betrug < 3 mg/kg.48 parts by weight of the dried butadiene graft rubber B were mixed with 52 parts by weight of granules of a commercially available styrene-acrylonitrile copolymer having an acrylonitrile content of 24 wt .-% and a viscosity of 64 at 250 ° C on a ZSK 30 twin-screw extruder extruded and granulated. The content of magnesium in the granules was <3 mg / kg, the content of calcium in the granules was <3 mg / kg.

Herstellung von Formmasse F-E (ABS):Production of molding compound F-E (ABS):

20 Gew.-Teile des getrockneten Butadien-Pfropfkautschuks B wurden mit 20 Gew.-Teilen eines Granulats eines handelsüblichen Styrol-Acrylnitril-Copolymers mit einem Acrylnitrilgehalt von 24 Gew.-% und einer Viskositätszahl von 64 und 60 Gew.-Teilen eines α-Methylstyrol-Acrylnitril-Copolymers mit einem Acrylnitrilgehalt von 30 Gew.-% und einer Viskositätszahl von 57 bei 250°C auf einem Zweiwellenextruder ZSK 30 extrudiert und granuliert. Der Gehalt an Magnesium im Granulat betrug < 3 mg/kg, der Gehalt an Calcium im Granlat betrug < 3 mg/kg.20 parts by weight of the dried butadiene graft rubber B were mixed with 20 parts by weight of a granule of a commercial styrene-acrylonitrile copolymer having an acrylonitrile content of 24 wt .-% and a viscosity number of 64 and 60 parts by weight of an α- Methyl styrene-acrylonitrile copolymer having an acrylonitrile content of 30 wt .-% and a viscosity number of 57 at 250 ° C on a twin-screw extruder ZSK 30 extruded and granulated. The content of magnesium in the granules was <3 mg / kg, the content of calcium in the granule was <3 mg / kg.

Herstellung von Vergleichsformmasse V-F-J (ASA):Preparation of comparative molding compound V-F-J (ASA):

45 Gew.-Teile des getrockneten Acrylat-Pfropfkautschuks H wurden mit 50 Gew.-Teilen eines Granulats eines handelsüblichen Styrol-Acrylnitril-Copolymers mit einem Acrylnitrilgehalt von 19 Gew.-% und einer Viskositätszahl von 100 bei 250°C auf einem Zweiwellenextruder ZSK 30 extrudiert und granuliert. Der Gehalt an Magnesium im Granulat betrug 370 mg/kg, der Gehalt an Calcium im Granulat betrug < 3 mg/kg.45 parts by weight of the dried acrylate graft rubber H were mixed with 50 parts by weight of granules of a commercial styrene-acrylonitrile copolymer having an acrylonitrile content of 19 wt .-% and a viscosity number of 100 at 250 ° C on a ZSK 30 twin-screw extruder extruded and granulated. The content of magnesium in the granules was 370 mg / kg, the content of calcium in the granules was <3 mg / kg.

Herstellung von Formmasse F-K (ASA):Production of molding compound F-K (ASA):

Die Herstellung von Formmasse F-K erfolgte wie die der Vergleichsformmasse V-F-J, wobei aber an Stelle des Acrylat-Pfropfkautschuks H der Acrylat-Pfropfkautschuk I eingesetzt wurde. Der Gehalt an Magnesium im Granulat betrug <3 mg/kg, der Gehalt an Calcium im Granulat betrug < 3 mg/kg.The production of molding compound FK was like that of the comparative molding compound VFJ, but instead of the acrylate graft rubber H, the acrylate graft rubber I was used. The content of magnesium in the granules was <3 mg / kg, the content of calcium in the granules was <3 mg / kg.

Herstellung von Vergleichsformmasse V-F-L (ASA):Preparation of comparative molding compound V-F-L (ASA):

45 Gew.-Teile des getrockneten Acrylat-Pfropfkautschuks H wurden mit 55 Gew.-Teilen eines Granulats eines handelsüblichen Styrol-Acrylnitril-Copolymers mit einem Acrylnitrilgehalt von 35 Gew.-% und einer Viskositätszahl von 80 bei 250°C auf einem Zweiwellenextruder ZSK 30 extrudiert und granuliert. Der Gehalt an Magnesium im Granulat betrug 360 mg/kg, der Gehalt an Calcium im Granulat betrug < 3 mg/kg.45 parts by weight of the dried acrylate graft rubber H were mixed with 55 parts by weight of granules of a commercially available styrene-acrylonitrile copolymer having an acrylonitrile content of 35 wt .-% and a viscosity number of 80 at 250 ° C on a ZSK 30 twin-screw extruder extruded and granulated. The content of magnesium in the granules was 360 mg / kg, the content of calcium in the granules was <3 mg / kg.

Herstellung von Formmasse F-M (ASA):Preparation of molding compound F-M (ASA):

Die Herstellung von Formmasse F-M erfolgte wie die der Vergleichsformmasse V-F-L, wobei aber an Stelle des Acrylat-Pfropfkautschuks H der Acrylat-Pfropfkautschuk I eingesetzt wurde. Der Gehalt an Magnesium im Granulat betrug <3 mg/kg, der Gehalt an Calcium im Granulat betrug < 3 mg/kg.The preparation of molding compound F-M was carried out as that of the comparative molding compound V-F-L, but instead of the acrylate graft rubber H, the acrylate graft rubber I was used. The content of magnesium in the granules was <3 mg / kg, the content of calcium in the granules was <3 mg / kg.

Herstellung von Vergleichsformmasse V-F-N (ASA/PC-Blend):Preparation of comparative molding compound V-F-N (ASA / PC blend):

20 Gew.-Teile des getrockneten Acrylat-Pfropfkautschuks H wurden mit 20 Gew.-Teilen eines Granulats eines handelsüblichen Styrol-Acrylnitril-Copolymers mit einem Acrylnitrilgehalt von 35 Gew.-% und einer Viskositätszahl von 80 und 60 Gew.-Teilen eines Granulats eines handelsüblichen Polycarbonats, Makrolon® 2800 der Bayer Material Science AG, bei 250°C auf einem Zweiwellenextruder ZSK 30 extrudiert und granuliert. Der Gehalt an Magnesium im Granulat betrug 135 mg/kg, der Gehalt an Calcium im Granulat betrug < 3 mg/kg.20 parts by weight of the dried acrylate graft rubber H were mixed with 20 parts by weight of a granules of a commercially available styrene-acrylonitrile copolymer having an acrylonitrile content of 35 wt .-% and a viscosity number of 80 and 60 parts by weight of granules commercially available polycarbonate, Makrolon ® 2800 from Bayer MaterialScience AG, extruded 30 at 250 ° C on a twin-screw extruder ZSK and granulated. The content of magnesium in the granules was 135 mg / kg, the content of calcium in the granules was <3 mg / kg.

Herstellung von Formmasse F-O (ASA/PC-Blend):Production of molding compound F-O (ASA / PC blend):

8,5 Gew.-Teile des getrockneten Acrylat-Pfropfkautschuks H wurden mit 8,5 Gew.-Teilen des getrockneten Acrylat-Pfropfkautschuks I, 13 Gew.-Teilen eines Granulats eines handelsüblichen Styrol-Acrylnitril-Copolymers mit einem Acrylnitrilgehalt von 19 Gew.-% und einer Viskositätszahl von 70 und 60 Gew.-Teilen eines Granulats eines handelsüblichen Polycarbonats, Makrolon® 2800 der Bayer Material Science AG, bei 250°C auf einem Zweiwellenextruder ZSK 30 extrudiert und granuliert. Der Gehalt an Magnesium im Granulat betrug 36 mg/kg, der Gehalt an Calzium im Granulat betrug < 3 mg/kg.8.5 parts by weight of the dried acrylate graft rubber H were mixed with 8.5 parts by weight of the dried acrylate graft rubber I, 13 parts by weight of a granule of a commercially available styrene-acrylonitrile copolymer having an acrylonitrile content of 19 wt. % and a viscosity number of 70 and 60 parts by weight of granules of a commercial polycarbonate, Makrolon ® 2800 of Bayer Material Science AG, extruded at 250 ° C on a twin-screw extruder ZSK 30 and granulated. The content of magnesium in the granules was 36 mg / kg, the content of calcium in the granules was <3 mg / kg.

Herstellung von Formmasse F-P (ASA/PC-Blend):Production of molding compound F-P (ASA / PC blend):

30 Gew.-Teile des getrockneten Acrylat-Pfropfkautschuks I wurden mit 10 Gew.-Teilen eines Granulats eines handelsüblichen Styrol-Acrylnitril-Copolymers mit einem Acrylnitrilgehalt von 19 Gew.-% und einer Viskositätszahl von 70 und 60 Gew.-Teilen eines Granulats eines handelsüblichen Polycarbonats, Makrolon® 2800 der Bayer Material Science AG, bei 250°C auf einem Zweiwellenextruder ZSK 30 extrudiert und granuliert. Der Gehalt an Magnesium im Granulat betrug <3 mg/kg, der Gehalt an Calcium im Granulat betrug < 3 mg/kg.30 parts by weight of the dried acrylate graft rubber I were with 10 parts by weight of a granulate of a commercially available styrene-acrylonitrile copolymer having an acrylonitrile content of 19 wt .-% and a viscosity number of 70 and 60 parts by weight of a Granules of a commercial polycarbonate, Makrolon ® 2800 from Bayer Material Science AG, extruded at 250 ° C on a twin-screw extruder ZSK 30 and granulated. The content of magnesium in the granules was <3 mg / kg, the content of calcium in the granules was <3 mg / kg.

Herstellung von Vergleichsformmasse V-F-Q (MABS):Preparation of comparative molding compound V-F-Q (MABS):

Es wurde ein Granulat eines handelsüblichen PMMA/ABS-Blends, Terlux® BX 13010 der BASF SE, eingesetzt. Der Gehalt an Magnesium im Granulat betrug 212 mg/kg, der Gehalt an Calcium im Granulat betrug < 3 mg/kg.It was 13010 BASF SE, used a granulate of a commercially available PMMA / ABS blends, Terlux ® BX. The content of magnesium in the granules was 212 mg / kg, the content of calcium in the granules was <3 mg / kg.

Meßmethoden:measurement methods: Bestimmung der Magnesium- und Calciumgehalte:Determination of magnesium and calcium contents:

Die Magnesium- und Calciumgehalte der obengenannten Formmassen F und der Vergleichsformmassen V-F wurden bestimmt, indem eine jeweils ausgewogene Menge des betreffenden Kunststoffgranulats verbrannt wurde, der Verbrennungsrückstand einem Soda-Borax-Aufschluß unterworfen wurde, anschließend der Aufschlußrückstand in Salzsäure gelöst wurde, und der Mg- und Ca-Gehalt der salzsauren Lösung mittels Atomemissionsspektrometrie mit induktiv gekoppeltem Plasma (ICP-AES) bestimmt wurde.The magnesium and calcium contents of the abovementioned molding compositions F and of the comparative molding compounds VF were determined by burning a respective balanced amount of the relevant plastic granulate, subjecting the combustion residue to soda-borax digestion, then dissolving the digestion residue in hydrochloric acid, and and Ca content of the hydrochloric acid solution was determined by inductively coupled plasma atomic emission spectrometry (ICP-AES).

Formteilherstellung und Formbelagsbildung:Molding production and shaping of moldings:

Zur Bestimmung der Formbelagsbildung bei der Formteilherstellung wurden die obengenannten Formmassen F und Vergleichsformmassen V-F als Granulat unter identischen Bedingungen in eine Spritzgießmaschine dosiert, aufgeschmolzen und in einer Zugstabs-Bindenaht-Form ohne Entgasungsöffnungen verspritzt. Das Anspritzen des Zugstabs erfolgte in dieser Form von den beiden Kopfseiten her, so daß sich die beiden Schmelzfronten in der Mitte der Form trafen und eine Bindenaht ergaben. Nach jeweils 500 Schüssen, d.h. spritzgegossenen Zugstäben, wurde die Form ausgebaut, die in der Umgebung der Bindenaht auftretenden Formbeläge visuell begutachtet und gemäß einer Skala von 1 (sehr gut, keine Formbeläge) bis 6 (mangelhaft, starke Formbeläge) beurteilt. Die jeweiligen Beurteilungen werden in Tabelle 1 widergegeben. Tabelle 1*: Beispiel Formmasse Ca-Gehalt der Formmasse [mg/kg] Mg-Gehalt der Formmasse [mg/kg] Beurteilung der Formbelagsbildung V-1 V-F-C <3 510 5 2 F-D <3 <3 2 3 F-E <3 <3 2 V-4 V-F-J <3 370 4-5 5 F-K < 3 <3 2 V-6 V-F-L <3 360 4-5 7 F-M <3 <3 2 V-8 V-F-N 11 135 3 9 F-O 5 36 2-3 10 F-P 8 <3 2 V-11 V-F-Q <3 212 4 * Beispiele und Formmassen mit vorangestelltem "V-" sind nicht erfindungsgemäß und dienen zum Vergleich In order to determine the formation of moldings in the production of moldings, the abovementioned molding compositions F and comparative molding compounds VF were metered as granules under identical conditions into an injection molding machine, melted and injection molded in a tie-rod / weld-joint shape without degassing openings. Injection of the tension rod was carried out in this form from the two head sides, so that the two enamel fronts met in the middle of the mold and gave a weld line. After every 500 shots, ie injection-molded tensile bars, the mold was removed, the moldings occurring in the vicinity of the weld line visually assessed and assessed according to a scale of 1 (very good, no moldings) to 6 (poor, strong moldings). The respective assessments are presented in Table 1. Table 1*: example molding compound Ca content of the molding compound [mg / kg] Mg content of the molding compound [mg / kg] Assessment of the formation of moldings V-1 VFC <3 510 5 2 FD <3 <3 2 3 FE <3 <3 2 V-4 VFJ <3 370 4-5 5 FK <3 <3 2 V-6 VFL <3 360 4-5 7 FM <3 <3 2 V-8 VFN 11 135 3 9 FO 5 36 2-3 10 FP 8th <3 2 V-11 VFQ <3 212 4 * Examples and molding compounds preceded by "V-" are not inventive and are for comparison

Die Beispiele belegen, daß die erfindungsgemäßen Verfahren zur Herstellung von Formteilen durch Formgebung thermoplastischer Formmassen F gegenüber den bekannten Verfahren eine verringerte Belagsbildung am Formgebungswerkzeug und/oder der Formteiloberfläche ausweisen.The examples show that the inventive method for the production of molded parts by molding thermoplastic molding compositions F compared to the known methods exhibit a reduced deposit formation on the forming tool and / or the molding surface.

Claims (7)

  1. A process for the production of moldings via shaping of thermoplastic molding compositions F with reduced formation of deposit on the shaping mold, wherein the thermoplastic molding compositions F comprise an amount of from 3 mg/kg to 75 mg/kg (calculated as the total of the mg of Mg and the mg of Ca per kg of thermoplastic molding composition F and determined by means of atomic emission spectrometry using inductively coupled plasma (ICPAES)) of at least one magnesium compound and/or calcium compound.
  2. The process according to claim 1, wherein the thermoplastic molding compositions F comprise, alongside the at least one magnesium compound and/or calcium compound,
    A) from 20 to 100% by weight of at least one impact-modified vinylaromatic copolymer selected from the group of acrylonitrile-butadiene-styrene copolymers (ABS), acrylonitrile-styrene-acrylate copolymers (ASA), and methacrylate-acrylonitrile-butadiene-styrene copolymers (MABS),
    B) from 0 to 80% by weight of at least one polycarbonate (PC), and
    C) from 0 to 60% by weight of further additives conventional in plastics,
    where each of the percentages by weight is based on the total weight of components A) to C) and the total of the percentages by weight is 100% by weight.
  3. The process according to claims 1 to 2, wherein the shaping takes place via extrusion to give pellets, foils, sheets, strands, or profiles.
  4. The process according to claims 1 to 2, wherein the shaping takes place via injection-molding to give moldings.
  5. The use of molding compositions F comprising an amount of from 3 mg/kg to 75 mg/kg (calculated as the total of the mg of Mg and the mg of Ca per kg of thermoplastic molding composition F and determined by means of atomic emission spectrometry using inductively coupled plasma (ICPAES)) of at least one magnesium compound and/or calcium compound, for reducing the formation of deposit on the shaping mold during the production of moldings.
  6. A molding that can be produced by one of the processes according to claims 1 to 4.
  7. A thermoplastic molding composition F for the production of moldings by processes according to claims 1 to 4, comprising an amount of from 3 mg/kg to 75 mg/kg (calculated as the total of the mg of Mg and the mg of Ca per kg of thermoplastic molding composition F and determined by means of atomic emission spectrometry using inductively coupled plasma (ICPAES)) of at least one magnesium compound and/or calcium compound.
EP08855931A 2007-12-04 2008-12-02 Method for producing molded parts having reduced deposit formation Revoked EP2219843B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08855931A EP2219843B1 (en) 2007-12-04 2008-12-02 Method for producing molded parts having reduced deposit formation

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07122265 2007-12-04
PCT/EP2008/066622 WO2009071537A2 (en) 2007-12-04 2008-12-02 Method for producing molded parts having reduced deposit formation
EP08855931A EP2219843B1 (en) 2007-12-04 2008-12-02 Method for producing molded parts having reduced deposit formation

Publications (2)

Publication Number Publication Date
EP2219843A2 EP2219843A2 (en) 2010-08-25
EP2219843B1 true EP2219843B1 (en) 2012-08-22

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EP08855931A Revoked EP2219843B1 (en) 2007-12-04 2008-12-02 Method for producing molded parts having reduced deposit formation

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US (1) US8481630B2 (en)
EP (1) EP2219843B1 (en)
KR (1) KR101551318B1 (en)
ES (1) ES2390805T3 (en)
WO (1) WO2009071537A2 (en)

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EP2841464B1 (en) 2012-04-23 2015-09-16 Bayer Materialscience AG Emulsion polymer containing compounds with improved surface after storage under warm and humid storage
AT16913U1 (en) * 2019-08-12 2020-12-15 Walter Kunststoffe Gmbh Compound additive for thermoplastics

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BRPI0909118A2 (en) 2008-03-22 2015-11-24 Bayer Materialscience Ag modified resilience polycarbonate compositions containing a good combination of raw tones, hydrolysis stability and melt stability.
EP2657258A1 (en) 2012-04-23 2013-10-30 Bayer MaterialScience AG Method for producing ABS compounds with improved surface after hot-wet storage
PL3473714T3 (en) 2012-06-08 2022-07-25 Dupont Nutrition Biosciences Aps Polypeptides having transgalactosylating activity
CN104955880B (en) 2013-02-07 2018-06-26 科思创德国股份有限公司 It is used to prepare the method for the ABS compositions after hot-wet storage with improved surface
KR20150115765A (en) 2013-02-07 2015-10-14 바이엘 머티리얼사이언스 아게 Method for the production of abs compositions having an improved surface
CN104968691B (en) 2013-02-07 2017-10-13 科思创德国股份有限公司 Method for preparing the ABS compositions with improved surface
KR102383487B1 (en) 2016-06-06 2022-04-05 이네오스 스티롤루션 그룹 게엠베하 Methods for producing stabilizer dispersions and methods for producing thermoplastic compositions stabilized by stabilizer dispersions
JP2023522334A (en) * 2020-04-15 2023-05-30 レゴ エー／エス Toy building blocks made from recycled ABS material
WO2024194289A1 (en) 2023-03-21 2024-09-26 Ineos Styrolution Group Gmbh Process for the preparation of a thermoplastic molding composition with good color stability

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US9670360B2 (en) 2012-04-23 2017-06-06 Covestro Deutschland Ag Emulsion polymer containing compounds with improved surface after storage under warm and humid storage
EP2841464B2 (en) † 2012-04-23 2020-10-28 Covestro Deutschland AG Emulsion polymer containing compounds with improved surface after storage under warm and humid storage
AT16913U1 (en) * 2019-08-12 2020-12-15 Walter Kunststoffe Gmbh Compound additive for thermoplastics

Also Published As

Publication number Publication date
US8481630B2 (en) 2013-07-09
KR101551318B1 (en) 2015-09-08
EP2219843A2 (en) 2010-08-25
US20100292385A1 (en) 2010-11-18
WO2009071537A3 (en) 2010-04-01
WO2009071537A2 (en) 2009-06-11
ES2390805T3 (en) 2012-11-16
KR20100095618A (en) 2010-08-31

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